Lube oil dispersant of improved odor and antioxidant properties

ABSTRACT

In the method of preparing sulfurized, alkoxylated, inorganic phosphorus acid free, steam hydrolyzed polyalkene-P2S5 reaction product useful as a detergent-dispersant in lubricating oil compositions of improved antioxidant and odor properties comprising contacting polyalkene and P2S5 in the presence of a catalytic amount of sulfur to form the polyalkene-P2S5 reaction product, contacting the resultant polyalkene-P2S5 reaction product with steam to form an inorganic phosphorus acid containing hydrolyzed polyalkene-P2S5 reaction product, removing inorganic phosphorus acid from the hydrolyzed polyalkene-P2S5 reaction product, contacting the inorganic acid free, hydrolyzed polyalkene-P2S5 reaction product with alkylene oxide, the improvement which comprises the step selected from the group consisting of (1) contacting said inorganic acid free, steam hydrolyzed polyalkene-P2S5 intermediate product with added sulfur, and (2) contacting the alkoxylated, inorganic phosphorus acid free, steam hydrolyzed polyalkene-P2S5 reaction product with added sulfur. The invention is also directed to the resultant sulfurized alkoxylated product and lubricant compositions thereof.

United States Patent [:91

Hellmuth et a1.

[ 1 Oct. 7, 1975 LUBE OIL DISPERSANT OF IMPROVED ODOR AND ANTIOXIDANTPROPERTIES [75] Inventors: Walter W. Hellmuth, Beacon; Harry Chaletz,Poughkeepsie; William P. Cullen, Fishkill, all of N.Y.

[73] Assignee: Texaco Inc., New York, NY.

[22] Filed: Feb. 9, 1973 [21] Appl. No: 330,914

Primary ExaminerH. Sneed Attorney, Agent, or Firm Thomas H. Whaley; CarlG. Ries; Robert A. Kulason [57] ABSTRACT In the method of preparingsulfurized. alkoxylated, in organic phosphorus acid free, steamhydrolyzed poly aIkene-P S reaction product useful as adetergentdispersant in lubricating oil compositions of improvedantioxidant and odor properties comprising contacting polyalkene and P 8in the presence of a catalytic amount of sulfur to form the poIyaIkene-PS reaction product, contacting the resultant pQlyaIkene-P S re actionproduct with steam to form an inorganic phosphorus acid containinghydrolyzed polyalkene-P S re action product, removing inorganicphosphorus acid from the hydrolyzed polyalkene-P S reaction product.contacting the inorganic acid free, hydrolyzed polyal kene-P S reactionproduct with alkylene oxide. the improvement which comprises the stepselected from the group consisting of (1) contacting said inorganic acidfree, steam hydrolyzed polyalkene-P s intermediate product with addedsulfur, and (2) contacting the alkoxylated, inorganic phosphorus acidfree, steam hydrolyzed polyalkene-P s reaction product with addedsulfur. The invention is also directed to the resultant sulfurizedalkoxylated product and lubricant compositions thereof.

10 Claims, N0 Drawings LUBE OIL DISPERSANT OF IMPROVED ODOR ANDANTIOXIDANT PROPERTIES BACKGROUND OF INVENTION Alkoxylated, inorganicphosphorus acid free, steam hydrolyzed polyalkene-P 5 reaction productsherein after also referred to as the alkoxylated product have long beenknown as superior detergent-dipsersants in lubricating oils. Thestandard method of preparation of these alkoxylated products is firstreacting a polyalkene with P 5 to form the polyalkene-P 8 reactionproduct, this reaction preferably conducted in the presence of acatalytic amount of sulfur, e.g., between about 0.1 and l wt. 71 tofacilitate the reaction. The resultant reaction product is thenhydrolyzed with steam followed by the removal of formed inorganicphosphorus acid byproducts therefrom. The steam hydrolyzed inorganicphosphorus acid free polyalkene-P 8 reaction product is then alkoxylatedto form the alkoxylated product. In the absence of inorganic acid thealkoxylation results in essentially a monoalkoxylated as opposed to apolyalkoxylated product. This resultant product has been characterizedin the past by the formula:

where R is hydrocarbyl and R and R are hydrogen or alkyl. Since theproduct in essence is a complex mixture of many compounds including ringcompounds containing phsophorus and sulfur in the ring as well asphosphoric and thiophosphoric structures, definition of the product interms of process appears suitable.

Although these prior alkoxylated products are excellentdctergenvdispersants, they have been evidencing some undesirableproperties when utilized in the recently developed high temperatureautomotive engines fitted with anti-pollution devices. Specifically,under the aforementioned conditions they appear to contribute to thesometimes substantial increase of lubricant compositions containingsame. Investigation has determined that this undesired oil thickening ispartially the result of the oxidative breakdown of the alkoxylateddetergenbdispersant triggered by excessibly high engine temperturescoupled with the funneling of ever increasing amounts of engine exhaustinto the crankcase for anti-pollution treatment. One means ofcounteracting this oxidative tendency was to include antioxidants in thelube formulations such as the alkylated diphenylamines. Although theadded antioxidants successfully retarded the oxidative decomposition ofthe alkoxylated product, they have the undesired feature of contributingto the excessive quantities of additives required in modern day engineoils as well as being another factor adding to the cost of said oils.

Another ever present problem with the alkoxylated products is the harshsulfurous odor evolving in the initial use of lubricating compositionscontaining said alkoxylated products. This odor is believed caused bythe evolution of volatile sulfurous materials loosely held in a chemicalsense in the reaction product. In the past, one means of removing theseobjectionable odors was to blow the products with nitrogen dioxide;however, such treatment places an undesirable burden on themanufacturing facilities in respect to control of the exiting nitrogenoxides in order to avoid atmospheric pollution.

Accordingly, objects of this invention are to provide a method toproduce a detergent-dispersant alkoxylated product of improved odorwhich is resistant to oxidative breakdowns in engine operation caused bythe strains of high temperature and anti-pollution devices placed onlubricating oils containing said alkoxylated product.

Another object is to provide a detergent-dispersant alkoxylated productof improved odor and oxidation resistant properties and lubricating oilcompositions thereof.

SUMMARY OF INVENTION We have discovered and this constitutes ourinvention a method, sulfurized alkoxylated product resulting therefromand lubricant compositions containing said sulfurized alkoxylatedproduct wherein said method produces a novel sulfurized alkoxylatedproduct of improved antioxidant and odor properties. Broadly, in themethod comprising first contacting in the presence of a catalytic amountof sulfur, polyalkene with P 8 to form polyalkene-P 5; reaction product,secondly contacting the resultant polyalkene-P 5 reaction product withsteam to form an inorganic phosphorus acid containing steam hydrolyzedpolyalkene-P 5 reaction product, thirdly removing the inorganicphosphorus acids from the steam treated reaction product, fourthlycontacting the inorganic acid free, steam hydrolyzed polyalkene-P 5reaction product with an alkylene oxide to form the alkoxylatedderivative, the improvement which comprises the step selected from thegroup consisting of (l) contacting the inorganic acid free, steamhydrolyzed polyalkene-P 8 reaction product with added sulfur at anelevated temperature and subjecting the resultant product to saidfourthly contacting and (2) contacting the alkoxylated inorganic acidfree, steam hydrolyzed polyalkene-P 8 final reaction product with addedsulfur at an elevated temperature, thereby forming the sulfurized,alkoxylated product of improved antioxidant and odor properties.

Hereinbefore and hereinafter the product formed by the method of theinvention will also be referred to as the sulfurized alkoxylatedproduct.

DETAILED DESCRIPTION OF THE INVENTION More specifically, in a methodcomprising:

a. first contacting a polyalkene of an average molecular weight betweenabout 500 and 50,000 with between about 5 and 40 wt. 7:. (basis reactionmixture) of P 8 in the presence of a catalytic amount of sulfur, e.g.,between about O.l and l wt. sulfur at a temperature between about I0Oand 320C, advantageously in an inert atmosphere, and diluting the finalproduct with a mineral lubricating oil,

b. secondly contacting the resultant lube concentrate of thepolyaIkene-P S reaction product with a stoichiometric excess of steam ata temperature between about l00 and 260C, preferably in an inertatmosphere, to form a lube concentrate of inorganic phosphorus acidcontaining steam hydrolyzed polyalkeneP S reaction product,

c. thirdly removing inorganic phosphorus acid from the steam treatedpolyalkene-P 5 reaction product to form the inorganic phosphorus acidfree, steam hydrolyzed polyalkene-P 5 reaction product,

d. fourthly contacting the inorganic acid free, steam hydrolyzedpolyalkene-P s reaction product with an alkylene oxide of from 2 to 10carbons at a temperature between about 180 and 220C, preferably in aninert atmosphere utilizing a mole ratio of alkylene oxide to initialpolyalkene of at least greater than about 1:1, preferably between about1:1 and 1:5,

the improvement which comprises the step selected from the groupconsisting of:

l. contacting the inorganic acid free, steam hydrolyzed polyalkene-P s,reaction product of step c with added sulfur, preferably in an inertatmosphere, at a temperature of between about 180 and 300C, preferablybetween 190 and 210C, utilizing a mole ratio of initial polyalkene toadded sulfur of between about 1:05 and 1:10, preferably between 1:1 and1:3, and then contacting the resultant sulfur treated product inaccordance with step (1" to form the sulfurized alkoxylated detergentproduct of improved antioxidant and odor properties.

contacting the alkoxylated final product ofd with added sulfur,preferably in an inert atmosphere at a temperature between about 130 and300C., preferably between 150 and 200C, utilizing a mole ratio ofinitial polyalkene to added sulfur of between about 1:0.5 and 1:10,preferably between 1 :l and 1:3, to form said sulfurized alkoxylateddetergent of improved antioxidant and odor properties.

STEP (1" In Step u the alkcnes from which the polyalkcne hydrocarbonreactants are derived are normally of 2 to 10 carbons such as ethylene,propylene, butylene, isobutylene, pentylene, hexylene, heptylene,isooctylene and decylene. Examples of the polyalkene are polybutene(polyisobutylene, polybutylene), polypropene (polypropylene) andcopolymers of alkenes such as propene-isobutene copolymer are preferredmaterials for reaction with P 8 In general, the polyalkene polymerreactants in copolymers have an average molecular weight between about500 and 50,000 but polymers and copolymers of a molecular weight between600 and 2000 are preferred. An example of one preferred polyalkene is apolyisobutene polymer having an average molecular weight of betweenabout 700 and 2000, most preferably about 1200. The polyalkene reactantpolymers contemplated herein are normally monoolefinic in nature.

The inert gas utilized to supply the non oxidizing atmosphere under themost preferred conditions in this and subsequent steps is usuallynitrogen.

The consistency of the catalytic sulfur employed ranges from powder tocoarse sand like particles with the liner consistencies being preferred.

At the end of this step, the polyalkene-P S product is advantageouslydiluted with a mineral lubricating oil desirably of an SUS viscositybetween about 50 and 1000 to form a lube concentrate polya1kene-P Sreaction mixture. Normally, sufficient lube oil is utilized to form aconcentrate having an oil content between about 10 and 90 wt. "/r,preferably between and 75 wt. "/1. Examples of the mineral lubricatingoil component contemplated herein are paraffin base, naphthene base ormixed paraffin base naphthene base distillates of residual oils. Thelubricating mineral oil bases generally have been subjected to solventrefining to improve lubricity and viscosity temperature relationship aswell as solvent dewaxing to remove waxy components and improve the pourof the oil. The preferred viscosities are normally between about and 300SUS at F.

In Step 12 the steam is usually passed directly into the oil solution.Under advantageous conditions, at least about 1 mole of steam isemployed per mole of polyalkeneP S reaction product and the hydrolysisis normally conducted for a period of between about 1 and 20 hours.

STEP c The hydrolyzed product derived from Step 1) contains undesirableinorganic phosphorus acid mixture, and they are removed by standardprocedures. A number of different procedures are available for theremoval of the inorganic sulfurous acid. In US. Pat. Nos, 2,951,835 and2,987,512 removal of the inorganic phosphorus acid is effected bycontact with synthetic anhydrous alkaline earth metal silicates andsynthetic anhydrous alkali metal silicates respectively. Further US.Pat. No. 3,135,729 describes a process where inorganic phosphorus acidsare removed from the hydrolyzed product by first drying the hydrolyzedproduct by passing an inert gas such as nitrogen therethrough at betweenabout and 200C. and then contacting the inorganic acids with anhydrousmethanol under mixing conditions at a temperature between about 40 and80C. in a methanol amount of between about 30 and 80 volume /t based onthe overall mixtures, thereby forming an extract phase containinginorganic phosphorus acid and a mineral oil raffinate phase containinginorganic phosphorus acid free, steam hydrolyzed P S -polyalkenereaction product. During the methanol extraction procedure,superatmospheric pressure may be applied, e.g., up to about 50 psig inorder to maintain the methanol in a liquid state. At the end of themethanol extraction step any methanol can ricd over into the raffinatephase is preferably removed, e.g., by stripping the ralfinate with aninert gas at an elevated temperature.

STEP d The inorganic phosphorus acid free, steam hydrolyzedpOlyalkene-P- S reaction product of Step c or the sulfurized versionthereof is contacted with alkylene oxide under essentially atmosphericor superatmospheric pressures, e.g., between about 10 and 500 psig beingadvantageous with the lower alkene oxides. Prior to contact with thealkylene oxide, the reaction mixture is preferably blown with inert gasand continued at a low level to aid the introduction of the alkyleneoxide. Excess alkylene oxide is desirably removed after com pletion ofthe reaction by blowing the reaction mixture at an elevated temperaturegenerally with an inert gas such as nitrogen.

The alkylene oxides contemplated herein are represented by the formula:

where R and R are hydrogen or aliphatic hydrocarbon radicals containingI to 6 carbons. Since there is no inorganic acid catalyst present suchas inorganic phosphorus acid byproduct (having been removed in Step theamount of alkylene oxide absorbed into the reaction system isessentially on a mole to mole basis in respect to initial polyalkenereactant. Alkylene oxide introduction is normally continued untilabsorption ceases usually in a period of l to hours. Hereinbefore andhereinafter what is intended by the term "initial polyalkcne" is thepolyalkene initially employed in Step at Specific examples of thealkylene oxides conternplated herein are ethylene oxide. propyleneoxide. 1,2- butylene oxide, 2.3butylene oxide. l,2- pentyleneoxide.2.3-pentylene oxide. l.2-hexylene oxide, 3-methyll .Z-pentylcne oxide,2.3-0ctylene oxide, 4-methyl-2.3-octylcne oxide, 4-methyl-l,2-hexyleneoxide, and 3-methyl-l.2-butylene oxide.

If odor improvement is desired in addition to that afforded by the addedsulfur improvement step, standard supplementary odor treatments may beemployed for still better consumer acceptance of the product. One suchmethod calls for the treatment of the unsulfurized product of Step (Iwith nitrogen dioxide or a mixture of nitrogen dioxide and oxygenoptionally diluted with inert gas such as nitrogen. The nitrogen dioxideand mixtures thereof are contacted, e.g., bubbled through with the Step1! product at a temperature between about 65 and 150C. until at leastabout 0. l5 wt. 1 ni trogen dioxide is absorbed. Under advantageousconditions, nitrogen dioxide is diluted with air or inert gas such asnitrogen, carbon dioxide and the like in a volume ratio of about 1:99.The residual oxides of nitrogen are removed from the treated mixture bystripping with an inert gas such as nitrogen or air.

IMPROVEMENT SULFURIZATION STEP l OR 2 In alternative improvement step Iand 2 the added sulfur employed as in the case of catalytic sulfurutilized in Step (I can be of a particle size ranging from powder tocoarse sand with the finer consistencies being preferred.

In all the foregoing steps the ingredients are preferably kept in anagitated state, when feasible, eg, via stirring in order to facilitateingredient contact.

SULFURIZED ALKOXYLATED PRODUCT AND LUBRICANT COMPOSITIONS THEREOF Asheretofore stated. the sulfurizcd alkoxylated products produced in theaforedcscribed procedure have usefulness as detcrgent-dispersants inautomotive lubricating oils. They are normally present in lubricatingoils in concentrations sufticient to impart detergentdispersantproperties thereto. In finished lubricants the concentration of thesulfurized alkoxylated product normally falls between about (].I and It)wt. 7r with a concentration between about I and 5 wt. 9% preferred.

In lubricating oil formulations of the invention the lubricating baseoils contemplated herein are those de scribed in respect toaforedescribed Step h. Further. the base oil constitutes a major amountof the finished formulation. cg, at least about 85 wt. 7! or more withthe remainder of the formulation being the sulfurized alkoxylatedproduct and supplementary additives to impart even greater oxidationresistance or other desirable properties thereto.

COOR

where R is an aliphatic radical of from I to 20 carbons and n is aninteger between about 600 and 35.000. One most suitable Vl improver isthe tetrapolymer of butyl inethacrylate, dodecyl methacrylate. octadecylmethacrylate and dimethylamine ethyl methacrylate being present in aweight ratio in the polymer of between about 4/10/5/1. The VI improversare normally employed in the finished lubricant product compositions inamounts between 0.1 and 3 wt. "/1.

One of the more commonly used supplementary lube oil corrosion inhibitorand supplementary antioxidant employed is divalent metal dialkyldithiophosphate resulting from neutralization of a P S,-,-alcoholreaction product with a divalent metal or divalent metal oxide. Bariumand Zinc dialkyl dithiophosphate are examples. Additional supplementaryantioxidants that may be employed are polyalkylated diphenylaminc and2,2'- diethyl-4-t-octyldiphcnylamine. These supplementary products areusually present in lubricating compositions in concentrations betweenabout U. l and 3 wt. "/0

A commonly used detergent-dispersant used as a supplement to thesulfonated alkoxylated products of the invention are the alkaline earthmetal alkylphenolates such as barium nonylphenolate, barium dodecyleresolate, calcium dodecylphenolate. Still other supplementaldetergcnt-dispersants are the calcium carbonate overbased calciumalkylsulfonatc formed by blowing a mixture of calcium hydroxide andcalcium alkylsulfonate, [c.g. calcium alkylbenzene sulfonate of about500 m.\v.l with carbon dioxide to form a product having a total basenumber (TBN) of 50 or more. e.g., 300 to 400. These supplementarydetergents are again usually present in the lubricating oil inconcentrations between about ().I and 5 wt. C4.

Still other ingredients found in the typical lubricant compositionscontemplated herein are antifoamants such as the dimethyl siliconepolymers in amounts of between about It) and 1000 ppm.

As heretofore indicated, it has been unexpectedly discovered thatemployment of the sulfurization im provemcnt step in the methodcontemplated herein, either immediately after the preparation of theinorganic phosphorus acid free, steam hydrolyzed polyalkene- P- Sreaction product prior to alkoxylation or directly after thealkoxylation step, unexpectedly substantially improved the antioxidantproperties of the sulfurized alkoxylated reaction product as well theodor properties. This improvement in some instances may be sufficient toeliminate the need of the inclusion of antioxidant additives in theformulation in which the sulfurized product is present and further mayin some instances eliminate the need for additional deodorizationtreatments. In any case, if an antioxidant and additional deodorizationtreatments are needed in respect to compositions containing thesulfurized alkoxylated products of the invention, the amount ofantioxidant required is essentially less than if the non sulfurizedproduct was employed and supplementary deodorization treatments can besubstantially less harsh for equivalent results. The economic benefitsfrom the elimination or reduction of supplementary antioxidant additiveuse and the elimination of added deodorization treatments or thereduction of the severity of such are obvious.

The following examples further illustrate the method, detergent productand lubricant compositions of the invention.

EXAMPLE 1 This example illustrates one of the alternative methods of theinvention and the sulfurized alkoxylated product resulting therefrom.

To a liter 3 necked flask fitted with a thermometer, condenser gas inlettube and mechanical stirrer there was charged 1320 grams (1.1 mole) ofpolyisobutenc having an average molecular weight of about 1200, 222grams (1.0 mole) of P 8 and 11 grams (0.34 gram atoms) sulfur. Thestirred mixture was heated to 230C. and held at that temperature for 5hours while maintained in a nitrogen atmosphere. The product was thencooled to 150C. and 2060 grams of naphthenic lubricating oil having anSUS viscosity of about 100 at 100F. were charged. The mixture was thenheated to 166C. and hydrolyzed with steam for hours. The resultant steamhydrolyzed product was then extracted with 2 liters of methanol at 60C.and the raffinate was stripped to 150C. with nitrogen blowing.

To a 3 liter 3-necked flask fitted with a stirrer, condenser, thermowelland thermocouple and gas inlet tubes there were charged 1315 grams (0.5mole) of stripped product and 32 grams l mole) of sulfur. The mixturewas stirred and the temperature was gradually raised to 200C. under acontinuous nitrogen purge and maintained at this temperature for 6hours. The sulfur treated mixture was allowed to cool to 90C. andethylene oxide bubbled therethrough until a vigorous reflux was noted inthe exit dry ice condenser. The amount of ethylene oxide absorbed was 44grams 1.0 mole). The flask was purged with nitrogen at 93C. for 1 hourand the purged material was then treated with nitrogen dioxide bybubbling nitrogen dioxide therethrough for a period of 2 hours followedagain by a nitrogen purge. The product was then filtered throughdiatomaceous earth. Analysis of the product found it to be a -40 wt. /1lube oil concentrate of sulfurized, monoethoxylated. inorganicphosphorus acid free, steam hydrolyzed polyisobutcne 1200 m.w. )-P Sreaction product having a sulfur content of 2.08 wt. /r, a phosphoruscontent of 0.83 wt. '71. a Neut. No. of 1.6, a Hydroxyl No.

EXAMPLE ll The procedure of Example 1 was repeated with the exceptionthat sulfurization took place at 175C. for a 4 hour period. Theresultant product was identified as -40 wt. 7r lube oil concentrate ofsulfurized, monoethoxylated, inorganic phosphorus acid free, steamhydrolyzed polyisobutene I200 m.w.)-P S reaction product having a sulfurcontent of 1.79 wt. a phosphorus content of 1.03 wt. 7:, a Neut. No. of3.3 and a Hydroxyl No. of 24.

EXAMPLE III This example illustrates the sulfurized alkoxylated productmethod and the alternative method of the invention wherein thesulfurization is conducted after alkoxylation.

To a 5 liter 3 necked flask fitted with a stirrer, condenser,thermowell, thermocouple and gas inlet tube there were charged 1320grams 1.1 mole) of polyisobutcne of a molecular weight of about 1200,222 grams (1.0 mole) P 5 and 11 grams (0.34 gram atoms) sulfur. Theresultant mixture was heated to 230C. and held at that temperature for 5hours while passing nitrogen therethrough to maintain the reactionmixture under a blanket of nitrogen. The product was then cooled to150C. and 2060 grams of naphthenic lubricating oil having an SUSviscosity of about at 100F. were introduced. The mixture was then heatedto 166C. and hydrolyzed with steam therein for a period of 10 hours.Steaming was conducted in a nitrogen atmosphere and the resultantproduct was dried by the passage of nitrogen therethrough at C. Thehydrolyzed product was extracted with -407n volume of methyl alcohol at60C. to give a methanol extract containing inorganic phosphorus acid anda raffinate containing inorganic phosphorus acid free, steam hydrolyzedpolybutene (1200 m.w.)-P S reaction product. The resultant raffinateproduct was heated to a temperature of 150C. for a -2 hour period. Themixture was then cooled to 93C. and ethylene oxide was bubbledtherethrough until a vigorous reflux was noted in the dry ice exitcondenser indicating that ethylene oxide was no longer being absorbed.The flask was then purged with nitrogen for a 1 hour period followed bya nitrogen dioxide blowing at 93C. until about 0.2 wt. 70 nitrogendioxide was absorbed. The resultant product was filtered throughdiatomaceous earth and identified as the lube concentrate ofmonoethoxylated polyisobutene (1200 m.w.)-P S;, reaction product.

To a 3 necked flask as described above there was charged 700 grams (0.25mole) of the filtered ethoxylated product together with 16.0 grams (0.5gram atom) sulfur. The mixture was stirred and the temperature raisedgradually to C. under a continuous nitrogen purge and maintained at thistemperature for a 4 hour period. The resultant product was analyzed anddetermined to be a -40 wt. naphthenic lubricating oil concentrate ofsulfurized ethoxylated, inorganic phosphorus acid free, steam hydrolyzedpolyisobutene 1200 m.w. )-P S reaction product having a sulfur contentof 1.87 wt. 70, phosphorus of 1.09 wt. Neut. No. of 1.52 and HydroxylNo. of 14.

EXAMPLE IV This example illustrates a comparative procedure, comparativeproduct and comparative lubricant composition of the prior art.

The procedure of Example 111 was repeated with the exception that thefinal sulfurization step was omitted. Analysis of the product determinedit to be -40 wt. naphthenic lubricating oil concentrate of amonoethoxylated inorganic phosphorus acid free, steam hydrolyzedpolyisobutene 1200 m.w. )"PgSy, reaction product having a sulfur contentof 0.86 wt. a phosphorus content of 1.06 wt. 7c, a Neut. No. of 3.1 wt.and a Hydroxyl No. of 14.

EXAMPLE v This example illustrates examples of the contemplated finishedautomotive lubricating oil compositions containing the sulfurizedalkoxylated product and further illustrates the superiority of thesulfurizcd alkoxylated product as opposed to its unsulfurizedcounterpart in respect to antioxidant properties and odor while beingessentially equivalent to the unsulfurized counterpart in respect todetergent-dispersant properties.

To test the lubricant compositions of the invention four tests wereemployed briefly described as follows:

BENCH OXIDATION TEST ENGINE OXIDATION TEST This test is used to evaluatemotor oils with respect to their ability to prevent high temperatureoxidative thickening. A single cylinder spark ignition engine of 42.5CID equipped with a fuel injection system, an air flow meter and apositive crankcase ventilation system is employed. Regualr leaded fuelis used to operate the engine under the following conditions:

50 3200125 6.0 :ltl

lfiil 241): 2 250:2 320:2 H5 Li): .I 2.01.2 2t): 2 41):: 2

Test Duration. Hrs.

Speed. RPM

Fuel Hon, lbs/hr.

Air:Fuel Ratio Jacket In. T.

Jacket ()ut F.

Oil (iallery. F.

Intake Air After Heater. F. Exhaust Back Pressure. in Hg. ('rankcase\':\e.. in H;.() Engine Ventilation, (FH Oil Pressure. PSI

number of hours to "break" the greater the resistance of the compositiontested to oxidative thickening.

ODOR TEST A panel of individuals rate the odor of the test sample as tothe degree of sulfur odor present. A rating of [0 denotes no sulfur odorand a rating of l denotes harsh hydrogen sulfide odor present. Theintermediate ratings are the degree of pungency of the sulfur odorlessening as the scale increases. The ratings given by each of the testpanel members are averaged and the average value reported as the odorrating.

BENCH SLUDGE TEST (BST) This test measures the relative detergencyproperties of the test sample. The test procedure comprises introducinginto cc. bottles portions of the sample composition titanium oxide (6wt. 7:) in oil. aqueous and hydrocarbon engine blowby. The bottles arethen agitated at elevated temperature for a period of time and a portionthereof is then centrifuged and observations are made of theprecipitated solid sediment bottom phase, the intermediate phasecomprising oil plus dispersed sediment and a clear top oil phase. Thesmaller the bottom sediment and top clear oil phase and the larger thedispersed intermediate phase, the greater the effectiveness of thedispersancy of the lubricant composition in maintaining the engineblowby products in the intermediate suspension. Test results (listed inTable III) refer to the depth of the bottom sediment in millimeters. Thesmaller the number (in. mm) the more effective the dispersant. A nondispersant oil would give a rating in excess of 3 mm.

EXAMPLE Va The lube concentrates of the ethoxylated products prepared inExamples I, II, III and IV were compounded into finished SAE lOW-3()type formulations of the following analysis:

TABLE I Ingredients Ex. IV

Refined paraffinic distillate Zinc isopropylmethylisubutyl carhinoldithiophosphate CO overbascd calcium 2 2 2 alkylated hen/.enc sulfonatc(TBN (1) Mineral oil concentrate con taining 40 wt. ,4 copolymer oflauryl and stenryl methacrylates (3:2 wt. ratio) Example I Cone. ExampleII Cone. Example lll Cone. Example IV Cone.

Oil Charge. lbs.

Spark Adumce. BT(' Motor oil performance is based on used oildegradation as determined by Differential Infrared analysis at 5 hourintervals. Performance is expressed in terms of hours to break, that is,the test time elapsed until the oil shows a sharp increase in the slopeof the Differential Infrared at 5.8 p. vs. time curve. The greater theTABLE II TABLE VI Visc sit (Kin. 38C,) Hrs, to Break Hrs. to BreakFormulation 24th Hr. 48th Hr. 72nd Hr. Formulation Vise. to Curve 5.8Curve A 37.9 86.0 i518 E 33 25 C 40 so m0 F 32 26 D 76.8 mm 214.8 G 2922 Formulations A, B. C and D were tested in the Bench We Claim: SludgeTest and as can be seen from the data in follow- In a th d f p epari g au ri at g l C n ning Table ill representative formulations A. B and Crate c ntaining between about l0 and 90 t. of a are essentiallyequivalent to comparative formulation rgen -disp r n lfurize lk xyla edpr D in respect to dispersancy properties: p g:

TABLE "I l a. first contacting a polyalkene of an average molecularweight between about 500 and 50,000 with P 5 t in the presence ofbetween about 0.1 and l wt. 7c Fmmuh'mn Scd'mcm Dcph (mm') sulfur at atemperature between about 100 and A 0.5 320C. and P 8 comprising betweenabout 50 and 2 40 wt. /0 of the reaction mixture,

D b. secondly diluting the polyalkene-P S with mineral lubricating oilto form a lube concentrate of between about l0 and 90 wt. of saidlubricating oil,

Formulations A. B, C and D were also subjected to c. thirdly contactingthe polyalkene-P s lube conthe odor test and as can be seen fromfollowing Table C nlrut t t am ill 11 mp rature t n IV representativeformulations A, B and C werejudged about 100 and 260C. utilizing atleast about a superior in odor to comparative formulation D: mole ratioexcess of steam in respect to said polyal- TABLE IV kene-P- S react onproduct.

d. fourthly removing inorganic phosphorus acid from the steam treatedpolyalkene-P S concentrate. Fmmumm Odor Rmmg e. fifthly contacting theinorganic acid free. steam by A 4 drolyzed polyalkene-PQS concentratewith an al- 2 l kylene oxide of the formula.

The following finished SAE formulations utilizing the where R and R arehydrogen or an alkyl containing 1 sulfurized alkoxylated lube oilconcentrate of Examples to 6 carbon atoms in a mole ratio of saidinorganic l and Ill and the unsulfurized comparative product ofphosphorus acid free, steam hydrolyzed P 3 Example IV were prepared andtheir compositions are polyalkcne reaction product to said alkyleneoxide of set forth below in following Table V with DOD repat least aboutl:l, the improvement which comprises resenting a known anti-oxidantadditive comprising the step of:

33% wt. "/2 2,2'-dicthyl-4'tertiary octyl diphenylamine contacting theinorganic acid free, steam hydrolyzed and 66% wt. 71 2,2-diethyl-44-dioctyl diphcnylamine: polyalkene-P s purified reaction product ofstep d with added sulfur at a temperature between about TABLE v 1 and300C. utilizing a mole ratio of added sul 50 fur: initial polyalkene ofbetween about l:0.5 and weight 0 1:10 with step *e" to form thesulfurized alkoxyl- E F G ated PI'OdUCt. ingredients Ex. I Ex. lll Ex.IV 2. A method in accordance with claim I conducted I in an inertatmosphere. if: 9 I u l g I '6 3. A method in accordance with claim 2wherein said zine isn m lmctl i i polyalkene is a polybutene of amolecular weight between about 500 and 2000 and said alk i 'd i phmc yene oxi e s DOD 0.35 ethylene oxide.

Example 1 n w 4. A method in accordance with claim 2 wherein saidExample lll (one 7 5 Emmpk. W 75 polyalkene is polyisobutene of amolecular weight of about i200 and said alkylene oxide is ethyleneoxide.

5. A lubricating oil composition comprising a major The preparedfinished formulations were subjected amount of lubricating oil andbetween about 0.1 and to the Engine Oxidation Test and as can be seen bythe 6% wt. "/1 of a detergent dispersant sulfurized alkoxylated data infollowing Table VI representative E and F were superior to thecomparative oxidation inhibited composition G in resistance tooxidation:

product contained in a between about 10 and 90 wt. '7( lubricating oilconcentrate thereof, said concentrate prepared by the method:

a. first contacting a polyalkcnc ofan average molecular weight betweenabout 500 and 50000 with P 8 in the presence of between about 0.1 and lwt. sulfur at a temperature between about l and 320C, said P 5comprising between about 5 and wt. /c of the reaction mixture.

b. secondly diluting the polyalkene-P S with mineral lubricating oil toform a lube concentrate of between about l0 and 90 wt. "/1 of saidlubricating oil,

c. thirdly contacting the polyalkene-P S, lube concentrate with steam ata temperature between about 100 and 260C. utilizing at least about amole ratio excess of steam in respect to said polyal- Rene-P 5 reactionproduct,

d. fourthly removing inorganic phosphorus acid from the steam treatedpolyalkene-P s concentrate,

e. fifthly contacting the inorganic acid free, steam hydrolyzedpolyalkeneP S concentrate with an alkylene oxide of the formula:

acid free, steam hydrolyzed P 5 the step of:

said method is conducted in an inert atmosphere.

7. A composition in accordance with claim 5 wherein said methodpolyalkene is polybutene of a molecular weight between about 500 and2000 and said alkylene oxide is ethylene oxide.

8. A composition in accordance with claim 5 wherein said method saidpolyalkene is poiyisobutene of a molecular weight of about 1200 and saidalkylene oxide is ethylene oxide.

9. A composition in accordance with claim 5 com prising a major amountof lubricating oil and between about 0. l and H) wt. 7( of saiddetergent dispersant sulfurized alkoxylated product.

10. A composition in accordance with claim 5 com prising a major amountof lubricating oil and between about l0 and wt. 7r of said detergentdispersant sulfurized alkoxylated product.

1. In a method of preparing a lubricating oil concentrate containingbetween about 10 and 90 wt. % of a detergent-dispersant sulfurizedalkoxylated product comprising: a. first contacting a polyalkene of anaverage molecular weight between about 500 and 50,000 with P2S5 in thepresence of between about 0.1 and 1 wt. % sulfur at a temperaturebetween about 100* and 320*C., and P2S5 comprising between about 50 and40 wt. % of the reaction mixture, b. secondly diluting thepolyalkene-P2S5 with mineral lubricating oil to form a lube concentrateof between about 10 and 90 wt. % of said lubricating oil, c. thirdlycontacting the polyalkene-P2S5 lube concentrate with steam at atemperature between about 100* and 260*C. utilizing at least about amole ratio excess of steam in respect to said polyalkene-P2S5 reactionproduct, d. fourthly removing inorganic phosphorus acid from the steamtreated polyalkene-P2S5 concentrate, e. fifthly contacting the inorganicacid free, steam hydrolyzed polyalkene-P2S5 concentrate with an alkyleneoxide of the formula:
 2. A method in accordance with claim 1 conductedin an inert atmosphere.
 3. A method in accordance with claim 2 whereinsaid polyalkene is a polybutene of a molecular weight between about 500and 2000 and said alkylene oxide is ethylene oxide.
 4. A method inacCordance with claim 2 wherein said polyalkene is polyisobutene of amolecular weight of about 1200 and said alkylene oxide is ethyleneoxide.
 5. A lubricating oil composition comprising a major amount oflubricating oil and between about 0.1 and 90 wt. % of a detergentdispersant sulfurized alkoxylated product contained in a between about10 and 90 wt. % lubricating oil concentrate thereof, said concentrateprepared by the method: a. first contacting a polyalkene of an averagemolecular weight between about 500 and 50,000 with P2S5 in the presenceof between about 0.1 and 1 wt. % sulfur at a temperature between about100* and 320*C., said P2S5 comprising between about 5 and 30 wt. % ofthe reaction mixture, b. secondly diluting the polyalkene-P2S5 withmineral lubricating oil to form a lube concentrate of between about 10and 90 wt. % of said lubricating oil, c. thirdly contacting thepolyalkene-P2S5 lube concentrate with steam at a temperature betweenabout 100* and 260*C. utilizing at least about a mole ratio excess ofsteam in respect to said polyalkene-P2S5 reaction product, d. fourthlyremoving inorganic phosphorus acid from the steam treatedpolyalkene-P2S5 concentrate, e. fifthly contacting the inorganic acidfree, steam hydrolyzed polyalkene-P2S5 concentrate with an alkyleneoxide of the formula:
 6. A composition in accordance with claim 5wherein said method is conducted in an inert atmosphere.
 7. Acomposition in accordance with claim 5 wherein said method polyalkene ispolybutene of a molecular weight between about 500 and 2000 and saidalkylene oxide is ethylene oxide.
 8. A composition in accordance withclaim 5 wherein said method said polyalkene is polyisobutene of amolecular weight of about 1200 and said alkylene oxide is ethyleneoxide.
 9. A COMPOSITION IN ACCORDANCE WITH CLAIM 5 COMPRISING A MAJORAMOUNT OF LUBRICATING OIL AND BETWEEN ABOUT 0.1 AND 10 WT. % OF SAIDDETERGENT SULFURIZED ALKOXYLATED PRODUCT.
 10. A composition inaccordance with claim 5 comprising a major amount of lubricating oil andbetween about 10 and 90 wt. % of said detergent dispersant sulfurizedalkoxylated product.